JP4269693B2 - Process for treating selenium mixture - Google Patents

Process for treating selenium mixture Download PDF

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JP4269693B2
JP4269693B2 JP2003006391A JP2003006391A JP4269693B2 JP 4269693 B2 JP4269693 B2 JP 4269693B2 JP 2003006391 A JP2003006391 A JP 2003006391A JP 2003006391 A JP2003006391 A JP 2003006391A JP 4269693 B2 JP4269693 B2 JP 4269693B2
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selenium
tellurium
copper
leaching
platinum
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JP2004218001A (en
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智 岡田
一祐 佐藤
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三菱マテリアル株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Description

【0001】
【発明の属する技術分野】
本発明は、セレンとテルルの混合物から効率よくセレンとテルルを分離する処理方法に関する。本発明の処理方法は、銅電解スライムから貴金属を回収するプロセスにおいて、金抽出後液を還元処理して得た還元滓からセレンテルルと白金族とを分離回収する処理工程において、セレンとテルルの分離方法として好適である。なお、本発明において、セレンテルル混合物とはセレンとテルルの混合物を意味し、例えば脱銅スライムからの金抽出後液から白金族含有残渣を濾別して得られる濾液を中和して生じる沈殿などである。また、セレンテルル白金族含有物とは少なくともセレンとテルルの何れかと白金族元素を含有するものを云い、セレンテルルとはセレンおよび/またはテルルを云う。
【0002】
【従来の技術】
銅製錬の銅電解工程では、電解液に不溶な不純物が残渣として副生する。この副生物中にはPt、Rh、Irなどの白金族元素、セレン、テルル、金、銀、銅がかなりの量含まれており、これらの金属を分離回収する方法がこれまで多数提案されている。例えば、白金族元素は、銀精錬工程からでる銀アノードスライムやこのスライムに硝酸を加えて金以外の金属成分を浸出した後に還元して得たスライムなどから回収されている。従来、これらのスライムを溶解するには、王水による溶解、塩酸と過酸化水素による溶解または塩酸と塩素ガス吹き込みによる溶解が利用されている。
【0003】
ところが白金族元素と共にセレンやテルルが共存しているセレンテルル白金族含有物の場合、これを還元して沈殿させると白金族元素がセレンテルルと化合物を形成してしまい、王水や塩酸および過酸化水素では溶解し難くなって分離回収ができなくなる欠点がある。とくに過酸化水素はセレン化物等の化合物表面で分解するため酸化剤としての効果を殆ど発揮することができない。また、このような化合物を焙焼して酸化セレンや酸化テルルの形で気化分離する方法があるが、その毒性による環境汚染の問題がある。
【0004】
銅電解澱物の金抽出後液に含まれる白金族元素とセレンテルルとを分離する方法として、液中の塩素イオン濃度を1.5モル/L以下とし、60〜90℃の温度下で8〜12%濃度の亜硫酸ガスを液中に吹き込み、白金族元素を還元して沈殿させる方法(特開2001−316735号)や、銅電解スライムの塩酸浸出液から溶媒抽出によって金および白金族を回収した抽出残液に二酸化イオウを導入し、セレンテルルを還元して沈殿させる方法(特許第3087758号、特開2001−207223号)などが知られている。
【0005】
しかし、これらの方法では、塩酸濃度、温度、亜硫酸ガス濃度、亜硫酸ガス量などのセレン還元時に制御するパラメータが多いため制御が難しく、白金族元素とセレンテルルの回収率が低下するなどの問題がある。さらに、二酸化イオウによる二段階還元処理は工程の管理が非常に難しく、しかも何れの沈殿においてもセレンテルルまたは白金族元素の混入が避けられず、二酸化イオウによる還元だけでは分離が不十分である。また、溶媒抽出によって白金族とセレンテルルとを分離する方法はコスト高であり、抽出後の回収処理も煩雑で手間がかかる欠点がある。
【0006】
さらに、銅電解スライムに対して塩酸および二酸化イオウ処理する代わりに硫酸酸性溶液で酸素富化ガス加圧条件下浸出処理する方法(特開平5−311258号)、銅電解スライムに硫酸酸性溶液で酸素富化ガス加圧条件下浸出処理した後、塩素イオン、チオ硫酸ナトリウム溶液処理して脱銀した後、銅を添加する方法(特開平5−311264号)も提案されている。しかし、このような酸素富化ガス加圧条件下に銅を使用する方法は工程管理が難しく、非常なコスト高になり、実用性は乏しいという欠点がある。
【0007】
この他に、酸化剤を用いて金属セレンを酸化し、これをアルカリ金属の炭酸塩または水酸化物で中和してアルカリ金属セレン酸塩を製造する方法(特開昭60−176908号)、セレン含有物をアルカリ金属炭酸塩と反応させて水溶性スラリーにし、これを酸化雰囲気下でばい焼してペレットにした後に水浸出する方法(特開昭56−5306号)、含テルル銅スライムを酸化剤の存在下に鉱酸に溶解し、これにアルカリを加えて銅を沈殿分離した後に中和してテルルを沈殿下する方法(特開昭56−84428号)、銅電解スライム等の原料に塩酸などの強酸処理し、化合物を含むものについては塩素などの酸化剤を併用し、テルルの抽出溶媒としてブチルカルビトールを使用する方法(特開2000−239753号)などが知られている。しかし、これらの方法は工程数が多く、しかも、セレンテルルのの回収効率が低い。
【0008】
さらに、テルルを回収する方法として、銅やニッケルの電解精製で得たアノードスライムを湿式処理して難溶性銀化合物を分離し、これをアンモニア等で浸出して銀を分離し、テルルを含有する残渣を炭酸ソーダで浸出する方法(特開2001−11547号)、金を溶媒抽出した際のテルル含有濾液を還元してセレンを析出させた後に硫酸加圧浸出に戻して脱銅浸出液に浸出させる方法(銅澱物湿式処理技術の確立、資源と素材、Vol.116, p.484,2000年)などがある。しかし、難溶性銀化合物からテルルを回収する方法はテルルの移行率が低いち云う問題がある。また、テルルを含む濾液を加圧浸出に戻す方法はテルルがメタル状であると浸出が不十分になり、プロセス内の滞留量が増えてしまうという問題がある。
【0009】
【発明が解決しようとする課題】
本発明は、従来の上記処理方法の問題を解決したものであり、セレンとテレルの混合物について、セレンおよびテレルを銅と合金化し、さらにこれを銅電解して電気銅を回収する一方、セレンおよびテルルをスライム化し、この銅電解スライムの浸出処理によってテルルを溶出してセレンと分離し、効率よくセレンとテルルを処理できるようにした処理方法を提供するものである。
【0010】
【課題を解決するための手段】
本発明は以下の構成からなるセレンテルル混合物の処理方法に関する。
〔1〕セレンテルル混合物を銅熔錬工程に導入してセレンおよびテルルと銅を合金化し、これを銅電解して電気銅を回収する一方、セレンおよびテルルを銅電解スライムに蓄積させ、この銅電解スライムを硫酸酸化浸出してテルルを溶出させることによって、テルルを浸出残渣に残るセレンと分離することを特徴とするセレンテルル混合物の処理方法。
〔2〕セレンテルル混合物が、銅製錬工程で得られるセレンとテルルおよび白金族の含有物を処理したものであって、銅製錬工程で得られる上記含有物を高温下でアルカリ浸出し、セレンおよびテルルを含む浸出液と白金族を含む浸出残渣とに分離するアルカリ浸出工程の後に、この浸出液に硫酸または塩酸を加えて中和し、生成した沈殿物である上記 [ ]に記載するセレンテルル混合物の処理方法。
〔3〕上記 [ ] の処理方法において、銅製錬工程で得られるセレンとテルルおよび白金族の含有物が、脱銅電解精錬スライムの塩酸浸出液から溶媒抽出によって金を分離した抽出残液の還元処理による沈澱物(還元処理滓)であるセレンテルル混合物の処理方法。
〔4〕上記 [ ] の処理方法において、銅製錬工程で得られるセレンとテルルおよび白金族の含有物が、脱銅電解精錬スライムの塩酸浸出液から溶媒抽出によって金を分離した抽出残液の還元処理滓をさらに処理したものであり、該還元処理によって先に沈澱したセレン滓をさらに蒸留した蒸留残をアルカリ溶融したもの、および上記セレン滓の後に沈澱したテルル滓をアルカリ浸出したものであるセレンテルル混合物の処理方法。
〔5〕上記[1]〜上記[4]の何れかに記載する処理方法において、銅電解スライムを硫酸酸化浸出してテルルを溶出させた後に、この浸出液を金属銅に接触させて生成したテルル化銅を回収するセレンテルル混合物の処理方法。
【0011】
【具体的な説明】
以下、本発明を具体的に説明する。
本発明の処理方法は、セレンテルル混合物を銅熔錬工程に導入してセレンおよびテルルと銅を合金化し、これを銅電解して電気銅を回収する一方、セレンおよびテルルを銅電解スライムに蓄積させ、この銅電解スライムを硫酸酸化浸出してテルルを溶出させることによって、テルルを浸出残渣に残るセレンと分離することを特徴とするセレンテルルの処理方法である。
【0012】
本発明の具体的な処理工程の一例を図1に示す。図示する処理方法は、セレンテルル混合物としてセレンテルル白金族含有物を用い、これを高温下でアルカリ浸出し、セレンテルルを含む浸出液と白金族を含む浸出残渣とに分離するアルカリ浸出工程の後に、この浸出液に硫酸または塩酸を加えて中和し、セレンテルル混合物を沈殿させ、この混合物を銅熔錬工程に導入してセレンおよびテルルと銅を合金化し、これを銅電解して電気銅を回収する一方、セレンおよびテルルを銅電解スライムに蓄積させ、この銅電解スライムを硫酸酸化浸出してテルルを溶出させることによって、テルルを浸出残渣に残るセレンから分離する。
【0013】
〔セレンテルル混合物〕
本発明の処理方法は、セレンテルル混合物として銅製錬工程でられるセレンテルル白金族含有物を処理したものを用いることができる。具体的には、セレンテルル白金族含有物として、例えば、脱銅電解精錬スライムの塩酸浸出液から溶媒抽出によって金を分離した抽出残液の還元処理滓などを原料として用いることができる。この脱銅電解スライムにはロジウム、ルテニウム、パラジウム、イリジウム、白金などの白金族元素、金、銀、セレン、テルルなどの有価金属が多量に含まれている。具体的には、セレンテルル白金族含有物は、例えば、脱銅精錬スライムを次のように処理して得られる。まず、脱銅精錬スライムを塩酸および過酸化水素によってスラリーにし、これを濾過して主に銀を含む浸出滓と、金、白金族元素およびセレン、テルルを含む浸出液とに分離する。次に、この浸出液の液性を調整し、DBC等を用いた溶媒抽出によって浸出液から金を分離する。このようにして金を分離した抽出残液には白金族元素およびセレン、テルルが液中に溶存している。そこで、この抽出残液に二酸化イオウ、具体的には例えば亜硫酸ガスを液中のセレン濃度を3g/L以上に保つ量で導入し、セレンを還元して沈殿させ、抽出残液から分離する。セレンを分離した濾液にさらに二酸化イオウを導入し、残りのセレンと共にテルルを還元して沈澱させ、濾別する。
【0014】
本発明はセレンテルル白金族含有物として上記金抽出後液の還元処理滓やさらに蒸留処理した蒸留滓を用いることができる。この他に、セレンテルル白金族含有液として、例えばメッキ工場の排水や製錬排水などのセレンテルルおよび白金族を含有する溶液を用いることができる。
【0015】
なお、上記金抽出後液の還元処理において、セレンとテルルを還元して沈澱させる際、テルルはセレンより還元電位が低く、セレンが沈澱した後にテルルが沈澱するので、セレン沈澱を濾別した後に、この濾液にさらに二酸化イオウを添加してテルルを沈澱化することによってセレンとテルルを分離回収することができる。この還元により白金族元素はセレン、テルルと共に沈殿する。
【0016】
このようにして得たセレンテルル白金族含有物を次のアルカリ浸出工程およびアルカリ溶融工程において処理する。この場合、上記抽出残液の還元によって先に沈澱したセレン滓を蒸留して高純度のセレンを回収し、残物(蒸留残)をアルカリ溶融処理し、その後に沈澱したテルル滓をアルカリ浸出処理するのが好ましい。この蒸留残はセレン化パラジウム等の化合物を形成しており、安定であるためアルカリ浸出してもセレンの溶出が進まない。蒸留滓をアルカリ溶融処理することによってセレンを効率よく処理することができる。一方、テルル滓中のロジウムおよびルテニウムはセレン滓中に含まれる場合よりも相対的に品位が高く、このためアルカリ溶融すると難溶性の酸化物になりやすく、後の塩酸浸出が難しくなる。従って、テルル滓はアルカリ浸出処理するのが好ましい。
【0017】
〔アルカリ浸出工程〕
セレンテルル白金族含有物をアルカリ浸出処理する。アルカリ浸出は1モル/L以上のアルカリ濃度下で行うのが良く、例えば5モル/L〜8モル/Lの範囲が好ましい。アルカリ濃度を1モル/L以上にすることによってpH14以上の強アルカリ性となり、セレンやテルルの酸化還元電位が下がり、常圧下において酸化剤を用いずに、セレンおよびテルルをアルカリ溶液中に溶出させることができる。なお、常温ではこのセレンやテルルの溶出反応の進行が遅いので、60℃以上の温度下、好ましくは80℃程度の温度下で浸出を行うのが適当である。
【0018】
上記アルカリ浸出によって、セレンおよびテルルはアルカリ溶液中に溶出してコロイド状に分散する。一方、ロジウムやパラジウムなどの白金族元素は溶出せずに残留する。これを濾別して、セレンないしテルルの浸出液と、白金族元素を含む固形分とに分離する。
【0019】
上記アルカリ浸出は、セレンテルル白金族含有物を蒸留処理した残物をアルカリ溶融して得た浸出液を加えて行っても良い。セレンテルル白金族含有物を還元処理して得たセレン滓またはこの還元セレン滓を蒸留処理して得た残物に、苛性ソーダ(NaOH)と硝酸ソーダ(NaNO3)の混合物からなるフラックスを添加し、これをフラックスの溶融温度(共晶温度)以上に加熱して溶融する。この加熱溶融によってセレンは主に4価になり、亜セレン酸ソーダ(Na2SeO3)を生じて溶解する。このアルカリ溶融によってセレンテルルが溶解し、これを水浸出してセレンテルルを含む浸出液と白金族を含む浸出残渣とに分離する。この浸出液をセレンテルル白金族含有物のアルカリ浸出工程に加えて前述のアルカリ浸出を行うことができる。このアルカリ溶融工程から得た浸出液を用いることによって、処理工程全体のセレンテルルの回収率を高めることができる。
【0020】
上記アルカリ浸出の固液分離後、セレンテルルを含む濾液に、硫酸または塩酸を加えて中和すると金属セレンないし金属テルルの黒色沈澱を生じ、溶液の色が濃紫色から次第に薄くなり、pH7付近で液は透明になる。これを固液分離することによって金属テルルおよび金属セレンの混合物を回収することができる。この混合物のセレンとテルルの品位は概ね99%以上であり、高品位の金属セレンないし金属テルルを回収することができる。なお、硫酸や塩酸に代えて硝酸を用いると、硝酸の酸化力によってセレンやテルルは酸化溶解するので沈殿化することができない。また、液温は60〜80℃が好ましい。この液温で中和すれば濾過性の良いセレンテルル混合物を得ることができる。
【0021】
本発明の処理方法は、上記セレンテルル混合物を銅熔錬工程に導入してセレンおよびテルルを銅と合金化し、この合金化した銅(粗銅)を電解工程に導入して電気銅を回収し、一方、セレンおよびテルルを他の不溶成分と共に銅電解スライムに蓄積させる。この銅電解は通常の銅電解条件下で実施することができる。銅電解によって高純度の電気銅を得る一方、セレンおよびテルルは粗銅に含まれる他の不溶成分と共に銅電解スライムになる。この銅電解スライムを硫酸で空気酸化して浸出処理(脱銅浸出)すると、スライムに含まれる銅とテルルの大部分が溶出する。この硫酸としては硫酸性電解液を用いることができる。溶出したテルルを含む脱銅浸出液を金属銅に接触させるとテルル化銅を形成するので、テルルをテルル化銅として回収することができる。工業的には溶出したテルルを含む脱銅浸出液を銅チップ塔に通液してテルル化銅を回収するとよい。一方、セレンは浸出残渣(脱銅スライム)中に残るので、この脱銅浸出によってセレンとテルルを分離することができる。
【0022】
上記脱銅浸出の後に、銅とセレンを含む浸出液は銅電解工程に戻して銅を電気銅として回収する。セレンは先に述べたように銅電解スライムに蓄積するので、この銅電解スライムの硫酸酸化浸出(脱銅浸出)を繰り返すことによって、セレンは脱銅スライムに濃縮される。また、この脱銅スライムには金、銀、白金族元素、鉛などの貴金属が多く含まれているので、この脱銅スライムに過酸化水素などの酸化剤と共に塩素ガス、塩酸などを導入して塩化浸出を行うことによって、これらの貴金属を溶解し、各貴金属元素に対応した処理工程を経て回収することができる。
【0023】
上記貴金属の回収工程の一例としては、上記塩化浸出によってスライム中の銀および鉛を塩化物に転じて不溶化する一方、金、白金族元素、セレン、テルルは浸出液中を溶解させ、この浸出液を金および白金族元素などを含有する浸出濾液と銀、鉛を含有する浸出濾滓(銀鉛含有滓)とに固液分離し、先に述べた処理工程などによって銀鉛含有滓から銀と鉛を分離回収する。また、テルルおよび白金族元素を含む浸出濾液から溶媒抽出によって金を分離し、還元して金を回収し、一方、その抽出残液を蒸留処理してセレン、テルルを還元し、この還元滓を用いて本発明の処理を繰り返すことによって、セレンおよびテルルを濃縮して効率よく回収することができる。
【0024】
【実施例】
セレンテルル還元澱物であるセレン白金族含有物(Se65%、Te30%、Pd5%、PtO.5%、Rh0.2%、RuO.4%)1kgに、5モル/Lの苛性ソーダ溶液10Lを混合し、80℃に保持してアルカリ浸出したところ、セレンおよびテルルの大部分は液中に溶解して液は濃い紫色になった。冷却後、濾過して残渣65gを回収した。この濾液の組成はSe:65g/L、Te:30g/Lであり、白金族元素は検出されなかった。この濾液を80℃に保持して硫酸(50%濃度)を加えpH1まで中和したところ、黒色粉末が沈殿した。この沈殿物の組成はSe:68.5%、Te:31.5%であった。また、濾液中のSeおよびTeの濃度はそれぞれ530ppmおよび210ppmであった。この沈殿物を銅熔錬工程に導入して電解精製し、生じたアノードスライムを硫酸性電解液で空気を吹き込んで浸出した。アノードスライム中のTeの大部分が溶け出すので浸出後のスライム中のTe品位は0.5%であった。また、Seは溶け出さないため浸出液中にSeは検出されず、浸出後のスライム中のSe品位は8.3%であつた。この浸出液を銅チップ塔に通液して、液中のTeをテルル化銅として回収した。またスライムに残留したSeや金を塩酸酸化浸出によって溶出させ、金を溶媒抽出した後に、この抽出後液に亜硫酸ガスを導入してセレンを還元し回収した。一方、先のアルカリ浸出残渣を分析したところ、Pd、Pt、Rh、Ruの白金族元素が主成分として確認され、その品位はPd:80%、Pt:8%、Rh:3%、Ru:6%であった。この残渣を塩酸2L、水500mLでリパルプし、液温を70℃に保ちながら、過酸化水素360mLを徐々に添加した。過酸化水素の添加終了後に冷却して濾過し、この濾液を分析したところ、Pd81g/L、Pt7g/L、Rh2.1g/L、Ru2.4g/Lであった。
【0025】
【発明の効果】
本発明の処理方法によれば、セレンテルル混合物を銅熔錬工程に導入してセレンおよびテルルを銅と合金化し、この銅合金を電解することによって高純度の電気銅を回収し、一方、セレンおよびテルルは銅電解スライムに蓄積されるので、これを硫酸酸化浸出(脱銅浸出)して、テルルを液中に浸出させてセレンと分離し、溶出したテルルを金属銅に接触させてテルル化銅として分離回収することができる。また、脱銅浸出残渣に残るセレンは、この残渣に含まれる金等の貴金属回収工程、例えば、金抽出五の還元処理工程において、分離回収することができる。
【図面の簡単な説明】
【図1】本発明の処理方法の概略を示す工程図。
[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a treatment method for efficiently separating selenium and tellurium from a mixture of selenium and tellurium. The treatment method of the present invention is a process for recovering noble metals from copper electrolytic slime, in a process for separating and recovering selenium tellurium and platinum group from reduced soot obtained by reducing the liquid after gold extraction. It is suitable as a method. In the present invention, the selenium tellurium mixture means a mixture of selenium and tellurium, such as a precipitate formed by neutralizing a filtrate obtained by filtering a platinum group-containing residue from a solution after gold extraction from decopper slime. . Further, the selenium tellurium platinum group-containing material means at least one of selenium and tellurium and a platinum group element, and selenium tellurium means selenium and / or tellurium.
[0002]
[Prior art]
In the copper electrolysis process of copper smelting, impurities insoluble in the electrolytic solution are by-produced as a residue. This by-product contains a considerable amount of platinum group elements such as Pt, Rh, Ir, selenium, tellurium, gold, silver, and copper, and many methods for separating and recovering these metals have been proposed. Yes. For example, platinum group elements are recovered from silver anode slime produced from the silver refining process, slime obtained by adding nitric acid to this slime and leaching metal components other than gold and reducing the same. Conventionally, in order to dissolve these slimes, dissolution by aqua regia, dissolution by hydrochloric acid and hydrogen peroxide, or dissolution by blowing hydrochloric acid and chlorine gas are used.
[0003]
However, in the case of a selenium tellurium platinum group-containing material in which selenium and tellurium coexist with the platinum group element, if this is reduced and precipitated, the platinum group element forms a compound with selenium tellurium, and aqua regia, hydrochloric acid and hydrogen peroxide. However, it is difficult to dissolve and cannot be separated and recovered. In particular, since hydrogen peroxide decomposes on the surface of a compound such as selenide, it can hardly exhibit the effect as an oxidizing agent. In addition, there is a method in which such a compound is roasted and vaporized and separated in the form of selenium oxide or tellurium oxide, but there is a problem of environmental pollution due to its toxicity.
[0004]
As a method for separating the platinum group element and selenium tellurium contained in the liquid after gold extraction of the copper electrolytic starch, the chlorine ion concentration in the liquid is 1.5 mol / L or less, and the temperature is from 60 to 90 ° C. A method in which 12% concentration sulfurous acid gas is blown into the liquid to reduce and precipitate the platinum group element (Japanese Patent Laid-Open No. 2001-316735), or extraction in which gold and platinum group are recovered by solvent extraction from a hydrochloric acid leaching solution of copper electrolytic slime A method of introducing sulfur dioxide into the residual liquid and reducing and precipitating selenium tellurium (Patent No. 3087758, JP-A No. 2001-207223) is known.
[0005]
However, these methods are difficult to control because there are many parameters to be controlled during selenium reduction such as hydrochloric acid concentration, temperature, sulfurous acid gas concentration, sulfurous acid gas amount, and there is a problem that the recovery rate of platinum group elements and selenium tellurium decreases. . Further, the two-stage reduction treatment with sulfur dioxide is very difficult to control the process, and in any precipitation, the mixing of selenium tellurium or platinum group elements cannot be avoided, and the reduction with sulfur dioxide alone is insufficient. Moreover, the method of separating the platinum group and selenium tellurium by solvent extraction is expensive, and has a drawback that the recovery process after extraction is complicated and laborious.
[0006]
Furthermore, instead of treating copper electrolytic slime with hydrochloric acid and sulfur dioxide, a method of leaching with a sulfuric acid acidic solution under an oxygen-enriched gas pressure condition (Japanese Patent Laid-Open No. 5-311258), copper electrolytic slime with a sulfuric acid acidic solution There has also been proposed a method (Japanese Patent Laid-Open No. 5-311264) in which copper is added after leaching under an enriched gas pressurization condition followed by treatment with a chlorine ion / sodium thiosulfate solution and desilvering. However, the method of using copper under such oxygen-enriched gas pressurization conditions has the disadvantages that process control is difficult, the cost is very high, and the practicality is poor.
[0007]
In addition, a method for producing an alkali metal selenate by oxidizing metal selenium using an oxidizing agent and neutralizing the metal selenium with an alkali metal carbonate or hydroxide (JP-A-60-176908), A method in which a selenium-containing material is reacted with an alkali metal carbonate to form a water-soluble slurry, which is baked in an oxidizing atmosphere to form pellets and then leached with water (Japanese Patent Laid-Open No. 56-5306). A method for dissolving tellurium by dissolving in mineral acid in the presence of an oxidant, adding an alkali thereto, precipitating and separating copper and then precipitating tellurium (JP-A-56-84428), raw materials such as copper electrolytic slime For example, a method using butyl carbitol as an extraction solvent for tellurium (JP 2000-239753) is known. That. However, these methods have many steps, and the recovery efficiency of selenium tellurium is low.
[0008]
Furthermore, as a method for recovering tellurium, the anode slime obtained by electrolytic purification of copper or nickel is wet-treated to separate a hardly soluble silver compound, which is leached with ammonia or the like to separate silver to contain tellurium. A method of leaching the residue with sodium carbonate (Japanese Patent Laid-Open No. 2001-11547), reducing the tellurium-containing filtrate obtained by solvent extraction of gold, precipitating selenium, and then returning to sulfuric acid pressure leaching and leaching into a copper removal leachate Methods (establishment of wet processing technology for copper starch, resources and materials, Vol.116, p.484, 2000). However, the method of recovering tellurium from a hardly soluble silver compound has a problem that the transfer rate of tellurium is low. Further, the method of returning the filtrate containing tellurium to the pressure leaching has a problem that if the tellurium is in a metal form, the leaching becomes insufficient and the amount of residence in the process increases.
[0009]
[Problems to be solved by the invention]
The present invention is a solution to the above-described conventional processing method, and in the case of a mixture of selenium and terel, selenium and terel are alloyed with copper and further electrolyzed to recover electrolytic copper. The present invention provides a treatment method in which tellurium is slimmed and the tellurium is eluted and separated from selenium by the leaching treatment of the copper electrolytic slime so that selenium and tellurium can be efficiently treated.
[0010]
[Means for Solving the Problems]
The present invention relates to a method for treating a selenium tellurium mixture having the following constitution.
[1] The selenium tellurium mixture is introduced into the copper smelting process to alloy selenium and tellurium with copper, and this is electrolyzed with copper to recover electrolytic copper, while the selenium and tellurium are accumulated in the copper electrolysis slime. A method for treating a selenium tellurium mixture , characterized in that tellurium is separated from selenium remaining in the leach residue by leaching the slime by sulfuric acid leaching.
[2] A selenium tellurium mixture is obtained by treating the selenium, tellurium and platinum group contents obtained in the copper smelting process, and the above-mentioned contents obtained in the copper smelting process are alkali leached at a high temperature to obtain selenium and tellurium. After the alkali leaching step for separating the leaching solution containing the platinum group and the leaching residue containing the platinum group, the leaching solution is neutralized by adding sulfuric acid or hydrochloric acid, and the resulting precipitate is treated with the selenium tellurium mixture described in [ 1 ] above Method.
In the processing method of [3] [2], content of selenium and tellurium and platinum group obtained in copper smelting process, reducing the decoppered electrolytic refining slime hydrochloric acid leachate raffinate separated gold by solvent extraction A method for treating a selenium tellurium mixture which is a precipitate (reduction treatment soot) by treatment.
In the processing method of [4] [2], content of selenium and tellurium and platinum group obtained in copper smelting process, reducing the decoppered electrolytic refining slime hydrochloric acid leachate raffinate separated gold by solvent extraction Selenium tellurium, which is obtained by further treating the treated soot, in which the distillation residue obtained by further distilling the selenium soot previously precipitated by the reduction treatment is alkali-melted, and the tellurium soot precipitated after the selenium soot is alkali-leached Method for processing the mixture.
[5] In the treatment method described in any one of [1] to [4] above, tellurium formed by contacting copper electrolytic slime with sulfuric acid leaching to elute tellurium and then contacting the leached solution with metallic copper A method for treating a selenium tellurium mixture for recovering copper halide.
[0011]
[Specific explanation]
Hereinafter, the present invention will be specifically described.
In the treatment method of the present invention, a selenium tellurium mixture is introduced into a copper smelting process to alloy selenium and tellurium with copper, and this is electrolyzed with copper to recover electrolytic copper, while selenium and tellurium are accumulated in copper electrolysis slime. The copper electrolysis slime is leached with sulfuric acid to elute tellurium, thereby separating tellurium from selenium remaining in the leaching residue.
[0012]
An example of specific processing steps of the present invention is shown in FIG. The illustrated treatment method uses a selenium tellurium platinum group-containing material as a selenium tellurium mixture, and this is leached with alkali at high temperature, and separated into a leachate containing selenium tellurium and a leach residue containing platinum group. Sulfuric acid or hydrochloric acid is added to neutralize, and a selenium tellurium mixture is precipitated. This mixture is introduced into a copper smelting process to alloy selenium and tellurium with copper, which is electrolyzed with copper to recover electrolytic copper. The tellurium is separated from the selenium remaining in the leaching residue by accumulating the tellurium and the tellurium in the copper electrolysis slime and eluting the copper electrolysis slime by sulfuric acid leaching.
[0013]
[Selenium tellurium mixture]
The processing method of this invention can use what processed the selenium tellurium platinum group-containing material obtained at a copper smelting process as a selenium tellurium mixture. Specifically, as a raw material for the platinum group containing selenium tellurium, for example, reduction residue of an extraction residue obtained by separating gold by solvent extraction from a hydrochloric acid leaching solution of decopperized electrolytic refining slime can be used as a raw material. The copper removal electrolytic slime contains a large amount of platinum group elements such as rhodium, ruthenium, palladium, iridium and platinum, and valuable metals such as gold, silver, selenium and tellurium. Specifically, the selenium tellurium platinum group-containing material is obtained, for example, by treating a copper removal smelting slime as follows. First, the decopper refining slime is slurried with hydrochloric acid and hydrogen peroxide, and is filtered to separate into a leach cake containing mainly silver and a leach solution containing gold, platinum group elements, selenium and tellurium. Next, the liquid property of the leachate is adjusted, and gold is separated from the leachate by solvent extraction using DBC or the like. Thus, the platinum group element, selenium, and tellurium are dissolved in the extraction residual liquid from which gold is separated. Therefore, sulfur dioxide, specifically, for example, sulfurous acid gas is introduced into the extraction residual liquid in an amount that keeps the selenium concentration in the liquid at 3 g / L or more, and selenium is reduced and precipitated, and separated from the extraction residual liquid. Sulfur dioxide is further introduced into the filtrate from which selenium has been separated, and tellurium is reduced and precipitated together with the remaining selenium, and is filtered off.
[0014]
In the present invention, as the selenium tellurium platinum group-containing material, the above-described gold-extracted solution-reduced soot or further distilled soot can be used. In addition, a solution containing selenium tellurium and a platinum group such as plating factory effluent and smelting effluent can be used as the selenium tellurium platinum group-containing liquid.
[0015]
In the reduction treatment of the solution after the gold extraction, when selenium and tellurium are reduced and precipitated, tellurium has a reduction potential lower than that of selenium, and tellurium precipitates after selenium precipitates. Selenium and tellurium can be separated and recovered by adding sulfur dioxide to the filtrate to precipitate tellurium. By this reduction, platinum group elements are precipitated together with selenium and tellurium.
[0016]
The selenium tellurium platinum group-containing material thus obtained is treated in the following alkali leaching step and alkali melting step. In this case, the selenium soot previously precipitated by the reduction of the extraction residue is distilled to recover high-purity selenium, the residue (distilled residue) is subjected to an alkali melting treatment, and then the tellurium soot precipitated is subjected to an alkali leaching treatment. It is preferable to do this. This distillation residue forms a compound such as palladium selenide, and is stable, so that selenium does not elute even when alkaline leaching occurs. Selenium can be efficiently treated by subjecting the distilled water to an alkali melting treatment. On the other hand, rhodium and ruthenium in tellurium are relatively higher in quality than those contained in selenium soot, so that when they are alkali-melted, they tend to be insoluble oxides and later leaching of hydrochloric acid becomes difficult. Therefore, tellurium is preferably subjected to alkali leaching treatment.
[0017]
[Alkaline leaching process]
Selenium tellurium platinum group-containing material is subjected to alkali leaching treatment. Alkaline leaching is preferably performed at an alkali concentration of 1 mol / L or more, and for example, a range of 5 mol / L to 8 mol / L is preferable. By increasing the alkali concentration to 1 mol / L or more, it becomes strongly alkaline with a pH of 14 or more, and the redox potential of selenium and tellurium is lowered, and selenium and tellurium are eluted in an alkaline solution without using an oxidizing agent under normal pressure. Can do. Since the elution reaction of selenium and tellurium is slow at room temperature, it is appropriate to perform leaching at a temperature of 60 ° C. or higher, preferably about 80 ° C.
[0018]
By the alkali leaching, selenium and tellurium are eluted in the alkali solution and dispersed in a colloidal form. On the other hand, platinum group elements such as rhodium and palladium remain without being eluted. This is separated by filtration and separated into a selenium or tellurium leachate and a solid containing a platinum group element.
[0019]
The alkali leaching may be performed by adding a leaching solution obtained by alkali-melting the residue obtained by distillation treatment of the selenium tellurium platinum group-containing material. To the selenium soot obtained by reducing the selenium tellurium-containing material or the residue obtained by distilling this reduced selenium soot, a flux comprising a mixture of caustic soda (NaOH) and sodium nitrate (NaNO 3 ) is added, This is heated and melted above the melting temperature (eutectic temperature) of the flux. By this heating and melting, selenium mainly becomes tetravalent, and soda selenite (Na 2 SeO 3 ) is generated and dissolved. This alkali melting dissolves selenium tellurium, which is leached with water and separated into a leachate containing selenium tellurium and a leach residue containing platinum group. This leaching solution can be added to the alkali leaching step of the selenium tellurium platinum group-containing material to perform the aforementioned alkali leaching. By using the leachate obtained from this alkali melting step, the recovery rate of selenium tellurium in the entire processing step can be increased.
[0020]
After solid-liquid separation of the above alkaline leaching, neutralization by adding sulfuric acid or hydrochloric acid to the filtrate containing selenium tellurium results in the formation of a black precipitate of metallic selenium or metallic tellurium, and the color of the solution gradually decreases from dark purple to a liquid near pH 7. Becomes transparent. A mixture of metal tellurium and metal selenium can be recovered by solid-liquid separation. The quality of selenium and tellurium in this mixture is approximately 99% or higher, and high-grade metal selenium or metal tellurium can be recovered. When nitric acid is used instead of sulfuric acid or hydrochloric acid, selenium and tellurium are oxidized and dissolved by the oxidizing power of nitric acid, and cannot be precipitated. The liquid temperature is preferably 60 to 80 ° C. If neutralized at this liquid temperature, a selenium tellurium mixture having good filterability can be obtained.
[0021]
In the treatment method of the present invention, the selenium tellurium mixture is introduced into a copper smelting process to alloy selenium and tellurium with copper, and the alloyed copper (crude copper) is introduced into an electrolysis process to recover electrolytic copper. Selenium and tellurium are accumulated in copper electrolytic slime along with other insoluble components. This copper electrolysis can be carried out under normal copper electrolysis conditions. While high purity electrolytic copper is obtained by copper electrolysis, selenium and tellurium become copper electrolytic slime together with other insoluble components contained in the crude copper. When the copper electrolytic slime is oxidized with sulfuric acid in air and leached (decopper leaching), most of copper and tellurium contained in the slime are eluted. A sulfuric acid electrolyte can be used as the sulfuric acid. When the copper removal leachate containing the eluted tellurium is brought into contact with metallic copper, copper telluride is formed, so that tellurium can be recovered as copper telluride. Industrially, copper telluride may be recovered by passing a copper removal leachate containing eluted tellurium through a copper chip tower. On the other hand, since selenium remains in the leaching residue (decopper slime), selenium and tellurium can be separated by this decopper leaching.
[0022]
After the copper removal leaching, the leaching solution containing copper and selenium is returned to the copper electrolysis step to recover copper as electrolytic copper. Since selenium accumulates in the copper electrolytic slime as described above, selenium is concentrated to the copper free slime by repeating the sulfuric acid oxidation leaching (copper leaching) of the copper electrolytic slime. Also, since this decopper slime contains a lot of precious metals such as gold, silver, platinum group elements, lead, etc., chlorine gas, hydrochloric acid, etc. are introduced into this decopper slime together with an oxidizing agent such as hydrogen peroxide. By performing leaching with chloride, these noble metals can be dissolved and recovered through a treatment process corresponding to each noble metal element.
[0023]
As an example of the recovery process of the precious metal, silver and lead in the slime are converted into chloride by the chlorination and insolubilization, while gold, platinum group elements, selenium and tellurium dissolve in the leachate, and the leachate is dissolved in gold. And leaching filtrate containing platinum group elements, etc. and leaching filter cake containing silver and lead (silver-lead containing rice cake), and separating silver and lead from the silver-lead containing rice cake by the treatment process described above. Separate and collect. Also, gold is separated from the leached filtrate containing tellurium and platinum group elements by solvent extraction and reduced to recover gold, while the extraction residue is distilled to reduce selenium and tellurium. By using and repeating the process of the present invention, selenium and tellurium can be concentrated and efficiently recovered.
[0024]
【Example】
1kg of selenium platinum group content (Se65%, Te30%, Pd5%, PtO.5%, Rh0.2%, RuO.4%), which is a reduced selenium tellurium, is mixed with 10 L of 5 mol / L sodium hydroxide solution. When the alkali leaching was maintained at 80 ° C., most of selenium and tellurium were dissolved in the liquid, and the liquid became dark purple. After cooling, the residue was filtered to recover 65 g of residue. The composition of this filtrate was Se: 65 g / L, Te: 30 g / L, and no platinum group element was detected. When this filtrate was kept at 80 ° C. and neutralized to pH 1 by adding sulfuric acid (50% concentration), black powder was precipitated. The composition of the precipitate was Se: 68.5% and Te: 31.5%. The concentrations of Se and Te in the filtrate were 530 ppm and 210 ppm, respectively. This precipitate was introduced into a copper smelting process and subjected to electrolytic purification, and the resulting anode slime was leached by blowing air with a sulfuric acid electrolyte. Since most of Te in the anode slime was dissolved, the Te quality in the slime after leaching was 0.5%. Further, since Se did not dissolve, Se was not detected in the leachate, and the Se quality in the slime after leaching was 8.3%. This leachate was passed through a copper chip tower, and Te in the liquid was recovered as copper telluride. Further, Se and gold remaining in the slime were eluted by hydrochloric acid leaching, and the gold was subjected to solvent extraction. Then, sulfur dioxide gas was introduced into the solution after extraction to reduce and recover selenium. On the other hand, when the previous alkali leaching residue was analyzed, platinum group elements of Pd, Pt, Rh, and Ru were confirmed as the main components, and the quality was Pd: 80%, Pt: 8%, Rh: 3%, Ru: It was 6%. This residue was repulped with 2 L of hydrochloric acid and 500 mL of water, and 360 mL of hydrogen peroxide was gradually added while maintaining the liquid temperature at 70 ° C. After the addition of hydrogen peroxide, the mixture was cooled and filtered, and the filtrate was analyzed. As a result, Pd was 81 g / L, Pt was 7 g / L, Rh was 2.1 g / L, and Ru was 2.4 g / L.
[0025]
【The invention's effect】
According to the treatment method of the present invention, a selenium tellurium mixture is introduced into a copper smelting process to alloy selenium and tellurium with copper, and the copper alloy is electrolyzed to recover high purity electrolytic copper, while selenium and Tellurium accumulates in copper electrolytic slime, so it is sulfated and leached (decopper leaching), tellurium is leached into the liquid and separated from selenium, and the eluted tellurium is contacted with metallic copper to form copper telluride. Can be separated and recovered. In addition, selenium remaining in the copper removal leach residue can be separated and recovered in a precious metal recovery process such as gold contained in the residue, for example, a reduction process of gold extraction five.
[Brief description of the drawings]
FIG. 1 is a process diagram showing an outline of a treatment method of the present invention.

Claims (5)

  1. セレンテルル混合物を銅熔錬工程に導入してセレンおよびテルルと銅を合金化し、これを銅電解して電気銅を回収する一方、セレンおよびテルルを銅電解スライムに蓄積させ、この銅電解スライムを硫酸酸化浸出してテルルを溶出させることによって、テルルを浸出残渣に残るセレンと分離することを特徴とするセレンテルル混合物の処理方法。The selenium tellurium mixture is introduced into the copper smelting process to alloy selenium and tellurium with copper, which is electrolyzed with copper to recover electrolytic copper, while the selenium and tellurium are accumulated in the copper electrolysis slime, which is then sulfated. A method for treating a selenium tellurium mixture , characterized in that tellurium is separated from selenium remaining in a leaching residue by leaching by oxidation to elute tellurium.
  2. セレンテルル混合物が、銅製錬工程で得られるセレンとテルルおよび白金族の含有物を処理したものであって、銅製錬工程で得られる上記含有物を高温下でアルカリ浸出し、セレンおよびテルルを含む浸出液と白金族を含む浸出残渣とに分離するアルカリ浸出工程の後に、この浸出液に硫酸または塩酸を加えて中和し、生成した沈殿物である請求項1に記載するセレンテルル混合物の処理方法。 The selenium tellurium mixture is obtained by treating the selenium, tellurium and platinum group contents obtained in the copper smelting process, and the above-mentioned contents obtained in the copper smelting process are alkaline leached at a high temperature, and a leaching solution containing selenium and tellurium 2. The method for treating a selenium tellurium mixture according to claim 1, which is a precipitate formed by adding sulfuric acid or hydrochloric acid to the leaching solution after the alkali leaching step for separating the leaching residue into a leaching residue containing platinum group.
  3. 請求項2の処理方法において、銅製錬工程で得られるセレンとテルルおよび白金族の含有物が、脱銅電解精錬スライムの塩酸浸出液から溶媒抽出によって金を分離した抽出残液の還元処理による沈澱物(還元処理滓)であるセレンテルル混合物の処理方法。3. The processing method according to claim 2, wherein the selenium, tellurium, and platinum group contents obtained in the copper smelting step are precipitates obtained by reducing the extraction residue obtained by separating the gold from the hydrochloric acid leachate of the copper free electrolytic refining slime by solvent extraction. The processing method of the selenium tellurium mixture which is (reduction processing paddle).
  4. 請求項2の処理方法において、銅製錬工程で得られるセレンとテルルおよび白金族の含有物が、脱銅電解精錬スライムの塩酸浸出液から溶媒抽出によって金を分離した抽出残液の還元処理滓をさらに処理したものであり、該還元処理によって先に沈澱したセレン滓をさらに蒸留した蒸留残をアルカリ溶融したもの、および上記セレン滓の後に沈澱したテルル滓をアルカリ浸出したものであるセレンテルル混合物の処理方法。3. The treatment method according to claim 2, wherein the selenium, tellurium and platinum group contents obtained in the copper smelting step further comprise a reduction treatment residue of the extraction residual liquid obtained by separating the gold from the hydrochloric acid leachate of the decopper electrolytic refining slime by solvent extraction. A method of treating a selenium tellurium mixture that has been treated and is obtained by further alkali-distilling the distillation residue obtained by further distilling the selenium soot previously precipitated by the reduction treatment, and by leaching the tellurium soot precipitated after the selenium soot .
  5. 請求項1〜4の何れかに記載する処理方法において、銅電解スライムを硫酸酸化浸出してテルルを溶出させた後に、この浸出液を金属銅に接触させて生成したテルル化銅を回収するセレンテルル混合物の処理方法。5. The selenium tellurium mixture for recovering copper telluride produced by bringing the leachate into contact with metallic copper after sulfuric acid leaching the copper electrolytic slime to elute tellurium in the treatment method according to claim 1 . Processing method.
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PCT/JP2003/003108 WO2003078670A1 (en) 2002-03-15 2003-03-14 Method for separating platinum group element
KR1020107002024A KR20100019577A (en) 2002-03-15 2003-03-14 Method for separating platinum group element
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CN038106884A CN1653198B (en) 2002-03-15 2003-03-14 Method for separating platinum group element
US10/506,613 US7479262B2 (en) 2002-03-15 2003-03-14 Method for separating platinum group element
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CA 2507370 CA2507370C (en) 2002-11-29 2003-08-28 Separation process for platinum group elements
ES03812271T ES2316871T5 (en) 2002-11-29 2003-08-28 Methods to separate platinum group elements from materials containing selenium / tellurium
EP20030812271 EP1577408B2 (en) 2002-11-29 2003-08-28 Method for separating platinum group elements from selenum/tellurium bearing materials
CA 2730558 CA2730558C (en) 2002-11-29 2003-08-28 Separation process for platinum group elements
DE60325639T DE60325639D1 (en) 2002-11-29 2003-08-28 METHOD FOR SEPARATING ELEMENTS OF THE PLATING GROUP FROM SELEN / TELLUR CONTAINING MATERIALS
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